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EP0186938B1 - Selbstaktivierender Hydrierkatalysator - Google Patents

Selbstaktivierender Hydrierkatalysator Download PDF

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Publication number
EP0186938B1
EP0186938B1 EP85306935A EP85306935A EP0186938B1 EP 0186938 B1 EP0186938 B1 EP 0186938B1 EP 85306935 A EP85306935 A EP 85306935A EP 85306935 A EP85306935 A EP 85306935A EP 0186938 B1 EP0186938 B1 EP 0186938B1
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EP
European Patent Office
Prior art keywords
catalyst
mixtures
catalyst according
ligand
sulphur
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Expired
Application number
EP85306935A
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English (en)
French (fr)
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EP0186938A1 (de
Inventor
Teh Chung Ho
Larry Eugene Mccandlish
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

Definitions

  • This invention relates to self-promoted molybdenum and tungsten sulphide hydrotreating catalysts.
  • this invention relates to self-promoted molybdenum and tungsten sulphide hydro-treating catalysts produced by heating one or more water soluble molybdate and/or tungstate catalyst precursors containing the promoter metal as part of the precursor molecule in the presence of sulphur at elevated temperature for a time sufficient to form said self-promoted catalyst.
  • feedstocks derived from these heavy materials contain more sulfur and nitrogen then feedstocks derived from more conventional crude oils.
  • feedstocks are commonly referred to as being dirty feeds.
  • These feeds therefore require a considerable amount of upgrading in order to obtain usable products therefrom, such upgrading or refining generally being accomplished by hydrotreating processes which are well-known in the industry.
  • Hydrotreating may be applied to a variety of feedstocks, e.g., solvents, light, middle, or heavy distillate feeds and residual feeds, or fuels.
  • hydrotreating processes In hydrotreating relatively light feeds, the feeds are treated with hydrogen, often to improve such compounds in the presence of hydrogen, which processes are collectively known as hydrotreating or hydrorefining processes, it being understood that hydrorefining also includes some hydrogenation of aromatic and unsaturated aliphatic hydrocarbons.
  • hydrotreating or hydrorefining processes processes are collectively known as hydrotreating or hydrorefining processes, it being understood that hydrorefining also includes some hydrogenation of aromatic and unsaturated aliphatic hydrocarbons.
  • US-A-2,914,462 discloses the use of molybdenum sulfide for hydrodesulfurizing gas oil
  • US-A-3,148,135 discloses the use of molybdenum sulfide for hydrorefining sulfur and nitrogen-containing hydrocarbon oils.
  • US ⁇ A ⁇ 2,715,603 discloses the use of molybdenum sulfide as a catalyst for the hydrogenation of heavy oils
  • US-A-3,074,783 discloses the use of molybdenum sulfides for producing sulfur-free hydrogen and carbon dioxide, wherein the molybdenum sulfide converts carbonyl sulfide to hydrogen sulfide.
  • Molybdenum and tungsten sulfides have other uses as catalysts, including hydrogenation, methanation, water gas shift, etc. reactions.
  • molybdenum and other transition metal sulfide catalysts as well as with other types of catalysts, higher catalyst surface areas generally result in more active catalysts than similar catalysts with lower surface areas. Thus, those skilled in the art are constantly trying to achieve catalysts that have higher surface areas. More recently, it has been disclosed in US-A-4,243,553, and US-A-4,243,554 that molybdenum sulfide catalysts of relatively high surface area may be obtained by thermally decomposing selected thiomolybdate salts at temperatures ranging from 300 ⁇ 800°C in the presence of essentially inert, oxygen-free atmospheres. Suitable atmospheres are disclosed as consisting of argon, a vacuum, nitrogen and hydrogen.
  • US ⁇ A ⁇ 4430443 describes and claims a process for the preparation of supported carbon-containing molybdenum sulfide and tungsten sulfide catalysts which comprises compositing a preselected quantity of a porous, refractory inorganic oxide with a salt characterized by the formula where B is an organo or hydrocarbyl substituted diammonium ion, an organo or hydrocarbyl substituted ammonium ion or quaternary ammonium ion, or an ionic form of a cyclic amine containing one or more basic N atoms, x is 1 where B is an organo or hydrocarbyl substituted diammonium ion, or 2 where B is an organo or hydrocarbyl substituted ammonium or quaternary ammonium ion or an ionic form of a cyclic amine containing one or more basic N atoms, M is molybdenum or tungsten, and y is 0, or a fraction or whole number
  • Catalysts made by the process of US-A-4430443 are prepared from solutions containing anions of thio- or oxythio-molybdates or tungstates and substituted ammonium or diammonium ions or ionic forms of cyclic amines containing one or more basic nitrogen atoms. None of the said ammonium or amine compounds is a chelating polydentate ligand.
  • self-promoted molybdenum and tungsten sulfide hydroprocessing catalysts are obtained by heating one or more water soluble catalyst precursors of the formula (ML)(MoYW1-104) in a non-oxidizing atmosphere in the presence of sulfur at an elevated temperature, preferably at a temperature of at least about 150°C, especially at least about 200°C, for a time sufficient to form said catalyst, wherein M comprises one or more divalent promoter metals preferably selected from Mn, Fe, Co, Ni, Cu, Zn and mixtures thereof, wherein y is any value ranging from 0 to 1, and wherein L is one or more, neutral, nitrogen-containing ligand at least one of which is a chelating polydentate ligand.
  • M comprises one or more divalent promoter metals preferably selected from Mn, Fe, Co, Ni, Cu, Zn and mixtures thereof, wherein y is any value ranging from 0 to 1, and wherein L is one or more, neutral, nitrogen-containing ligand at least
  • ligand L will have a denticity of six and will be either three bidentate or two tridentate chelating, alkyl amine ligands, M will be selected from Ni, Fe, Co and mixtures thereof and the non-oxidizing atmosphere will contain hydrogen sulfide as the source of sulfur.
  • Hydroprocessing is meant to include any process that is carried out in the presence of hydrogen, including, but not limited to, hydrocracking, hydrodenitrogenation, hydrodesulfurization, hydrogenation of aromatic and aliphatic unsaturated hydrocarbons, methanation, water gas shift, etc. These reactions include hydrotreating and hydrorefining reactions, the difference generally being thought of as more of a difference in degree than in kind, with hydrotreating conditions being more severe than hydrorefining conditions. Some of the catalysts of this invention have hydrotreating or hydrorefining activities substantially greater than that of conventional hydrotreating catalysts such as cobalt molybdate on alumina.
  • the catalysts of this invention may be used in bulk form or supported on a suitable inorganic refractory oxide support such as alumina.
  • a suitable inorganic refractory oxide support such as alumina.
  • a particularly significant advantage of this invention is that the water solubility of the catalyst precursor permits the precursor to be impregnated onto a suitable support such as alumina, via conventional impregnation techniques such as incipient wetness and adsorption.
  • the catalyst precursor is a water soluble metallate having the formula wherein M is one or more divalent promoter metals preferably selected from Mn, Fe, Co, Ni, Cu, Zn and mixtures thereof.
  • M is one or more divalent promoter metals preferably selected from Mn, Fe, Co, Ni, Cu, Zn and mixtures thereof.
  • M will be selected from
  • the promoter metal may be a mixture of two, three, four, five or even six promoter metals.
  • the precursor will have the formula [(Ni a Co 1-a )L] (MoyW l -,0 4 ) wherein 0 ⁇ a ⁇ 1.
  • the precursor may be a self promoted molybdate, tungstate or combination thereof. If it is only a molybdate it is obvious that y will have a value of 1. Alternatively, if the precursor is a tungstate y will be zero.
  • the ligand L will generally have a denticity of six and will be one or more neutral, nitrogen containing ligands wherein at least one of said ligands is a multidentate chelating ligand which chelates the promoter metal cation to form a chelated promoter metal cation [ML] 2+.
  • the catalytic metal oxide anion (Mo y W 1-y O 4 ) 2- will be ionically bound to the chelated promoter metal cation [ML] 2+ .
  • neutral is meant that the ligand itself does not have a charge.
  • ligand is used to designate functional coordinating groups which have one or more pairs of electrons available from the formation of coordinate bonds.
  • Ligands that can form more than one bond with a metal ion are called polydentate while ligands that can form only one bond with a metal ion are called monodentate.
  • Monodentate ligands are not capable of forming chelates.
  • L will be one or more polydentate chelating ligands.
  • the denticity of the ligand L will generally be six, because the promoter metal cations prefer six-fold coordination. Hence, if more than one species of ligand is employed in the precursor molecule, the denticity of the ligand species will usually add up to six. It should be understood that it is possible for ligand L to have a total denticity of less than six, but in most cases L will have a total denticity of six.
  • L will be three bidentate ligands, two tridentate ligands, a mixture of a bidentate and a quadridentate ligand, a hexadentate ligand or a mixture of a polydentate ligand with a monodentate ligands as long as the combination has a total denticity of six.
  • the ligands useful in this invention include alkyl and aryl amines and nitrogen heterocycles. Illustrative but non-limiting examples of ligands useful in the catalyst precursors of this invention are set forth below.
  • Monodentate ligands will include NH 3 as well as alkyl and aryl amines such as ethyl amine, dimethyl amine, pyridine, etc.
  • Useful chelating bidentate amine ligands are illustrated by ethylene-diamine, 2,2'-bipyridine, 1,10-phenylene bis(dimethyl-amine), o-phenylene diamine, tetramethylethylenediamine and propane-1,3 diamine.
  • useful chelating tridentate amine ligands are represented by terpyridine and diethylenetriamine while triethylenetetramine is illustrative of a useful chelating quadradentate amine ligand.
  • Useful chelating pentadentate ligands include tetraethylenepentamine while sepulchrate (an octazacryptate) is illustrative of a suitable chelating hexadentate ligand.
  • sepulchrate an octazacryptate
  • polydentate alkyl amines for L.
  • alkyl amines that are useful in the catalyst precursor of this invention include ethylenediamine, diethylenetriamine, and tetraethylenetetramine. It is particularly preferred to use bidentate and tridentate alkyl amines such as ethylenediamine and diethylenetriamine.
  • the precursor salts useful for forming the catalysts of this invention may be prepared by mixing an aqueous solution of ammonium molybdate and/or tungstate with an aqueous solution of the chelated promoter metal cation [ML]2+ which, in the presence of excess metallate, ligand and/or chelated promoter metal cation, will result in the formation of the precursor salt as a precipitate which is readily recovered.
  • the chelating promoter cation is easily formed by, for example, mixing an aqueous solution of one or more water soluble promoter metal salts with the ligand.
  • the water soluble salt may be any water soluble salt that is convenient to use such as a halide, sulfate, perchlorate, acetate, nitrate, etc.
  • an aqueous solution of ammonium molybdate and/or tungstate may be mixed with the ligand and the resulting solution mixed with an aqueous solution of promoter metal salt or the salt can be added to the ligand and dissolved into the solution of molybdate and/or tungstate.
  • the catalyst precursor preparation will be further understood by reference to the Examples, infra.
  • the catalysts of this invention may be used in bulk or supported on a suitable support, preferably supported on a suitable inorganic refractory oxide support such as alumina.
  • a suitable support preferably supported on a suitable inorganic refractory oxide support such as alumina.
  • an advantage of the catalyst precursors useful in this invention resides in their water solubility which permits them to be supported on suitable support materials by techniques well-known in the art, such as impregnation, incipient wetness and the like, the choice being left to the convenience of the practitioner.
  • the impregnation technique the aqueous impregnation solution will be contacted with the support for a time sufficient to deposit the precursor material onto the support either by selective adsorption or alternatively, the excess water may be evaporated during drying, leaving behind the precursor salt.
  • the incipient wetness techniques may be used whereby just enough of an aqueous precursor salt solution is added to dampen and fill the pores of the support.
  • the catalysts of this invention may be prepared by heating one or more catalyst precursor salts, bulk or supported, in the presence of sulfur in a non-oxidixing atmosphere, at a temperature of at least about 200°C for a time sufficient to form the catalyst.
  • sulfur required during the formation of the catalyst will be present in the form of a sulfur bearing compound and in an amount in excess of that required to form the catalyst.
  • the catalyst be formed by heating the precursor in the presence of sulfur or, preferably in the presence of a sulfur bearing compound which can be one or more solids, liquids, gases or mixtures thereof. Mixtures of hydrogen and H 2 S have been found to be particularly preferred.
  • the temperature will range between from about 250 ⁇ 600°C, more preferably from about 250-500°C and still more preferably from about 300-400°C.
  • the non-oxidizing atmosphere may be inert or net reducing.
  • hydrotreating conditions vary considerably depending on the nature of the hydrocarbon being hydrotreated, the nature of the impurities or contaminants to be reacted or removed, and, inter alia, the extent of conversion desired, if any.
  • a naphtha boiling within a range of from about 25°C to about 210°C a diesel fuel boiling within a range of from about 170°C to 350°C
  • a heavy gas oil boiling within a range of from about 325°C to about 475°C a lube oil boiling within a range of from about 290-500°C, or residuum containing from about 10 percent to about 50 percent of material boiling above about 575°C.
  • a tris(ethylenediamine) nickel molybdate Ni(en) 3 MoO 4 catalyst precursor was prepared by dissolving ammonium molybdate into ethylenediamine (en) and the resulting solution cooled to 0°C in an ice bath. An aqueous solution of nickel chloride was slowly added, in aliquots, to the above solution, with agitation after the addition of each aliquot. A precipitate was formed and recovered by vacuum filtration. This precipitate was Ni(en)gMo0 4 and was washed with distilled water and acetone and then dried in a vacuum oven at 50°C for three hours. The resulting cake was screened, pelletized, sized to 20/40 mesh (Tyler) (0.833 to 0.0164 mm).
  • the pelletized catalyst precursors were placed into a stainless steel reactor at 100°C at atmospheric pressure where they were purged for one hour under nitrogen. Ten percent of hydrogen sulfide in hydrogen was introduced into the reactor at a space velocity of 0.75 SCF/h (0.1336 IH 2 per I oil) for each 10 cm 3 of catalyst in the reactor. The temperature in the reactor was then raised to 325-360°C and kept at this temperature for one to three hours to form the catalyst after which the temperature in the reactor was lowered to 100°C, the H 2 S/H 2 gas flow was stopped and the reactor was purged with nitrogen until room temperature was reached.
  • each catalyst was loaded into a stainless steel, fixed-bed reactor.
  • the conditions in the reactor were as set forth below:
  • the liquid product was analyzed for sulfur by X-ray fluorescence and for nitrogen by combustion analysis.
  • the feedstock used was a light catalytic cycle oil (LCCO) that was about 20 wt.% paraffinic having properties set forth in Table 1.
  • LCCO light catalytic cycle oil
  • the nickel molybdenum catalyst is sold under the tradename HCD by American Cyanamid Company, Stamford, Connecticut, United States of America. These catalysts were sulfided by employing the same procedures used to form the catalysts of this invention, except that the temperature was 360°C for one hour.
  • the LCCO feed was hydrotreated at LHSV ranging from 1 to 6 with a catalyst prepared by impregnating a chromia on alumina support material with a Ni(en) 3 Mo0 4 salt.
  • This impregnate was then ground, pelletized and sulfided at 360°C for one hour following the procedure for Examples 1-3.
  • This catalyst gave a %HDS of 70.5 and % HDN of 56.6 when tested with the LCCO feed at 325°C, 3.15 MPa and 3,000 SCF (84.95 m 3 ) of hydrogen per bbl (158.97 I) of oil at an LHLSV of 3.0.
  • the final catalyst was sulfided at 400°C for one hour with a 10% H2Sin hydrogen mixture, following the procedure for Examples 1-3.
  • This catalyst gave a % HDS of 58.1 and % HDN of 31.3 when tested with the LCCO feed at 325°C, 3.15 MPa and 3000 SCF (84.95 m 3 ) of hydrogen per bbl (158.97 I) of oil at an LHSV of 3.0.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (17)

1. Selbstaktivierter Molybdän- und/oder Wolframsulfid-Katalysator, gebildet durch ausreichend langes Erhitzen auf eine erhöte Temperatur von einem oder mehreren Katalysatorvorläufern in einer nichtoxydierenden Atmosphäre in Gegenwart von Schwefel, dadurch gekennzeichnet, daß der (die) Katalysatorvorläufer die Formel (ML)(MoyW1-yO4) hat (haben), in der M ein oder mehrere zweiwertige Promotormetalle umfaßt, y ein Wert im Bereich von 0 bis 1 ist und L ein oder mehrere neutrale stickstoffhaltige Liganden, von denen mindestens einer ein chelatisierender mehrzähniger Ligand ist, bedeutet.
2. Katalysator nach Anspruch 1, bei dem M ein oder mehrere zweiwertige Promotormetalle ausgewählt aus Fe, Co, Ni, Zn, Cu, Mn und deren Mischungen umfaßt.
3. Katalysator nach Anspruch 2, bei dem das Promotormetall M ein oder mehrere zweiwertige Metalle ausgewählt aus (a) Fe, Co, Ni und deren Mischungen und (b) Mischungen von (a) mit Zn, Cu, Mn oder Mischungen derselben umfaßt.
4. Katalysator nach Anspruch 3, bei dem M aus Ni, Fe, Co und Mischungen derselben ausgewählt ist.
5. Katalysator nach einem der vorangehenden Ansprüche, in dem der Schwefel in Form einer oder mehrerer schwefeltragender Verbindungen vorliegt.
6. Katalysator nach einem der vorangehenden Ansprüche, bei dem der Ligand L aus Alkylaminen, Arylaminen, Stickstoffheterocyclen und deren Mischungen, vorzugsweise aus einem Alkylamin, ausgewählt ist.
7. Katalysator nach einem der vorangehenden Ansprüche, bei dem der Ligand L eine Gesamtzähnigkeit von 6 aufweist.
8. Katalysator nach einem der vorangehenden Ansprüche, bei dem der Ligand im wesentlichen aus zwei dreizähnigen Liganden und drei zweizähnigen Liganden ausgewählt ist.
9. Katalysator nach einem der vorangehenden Ansprüche, wobei überschüssiger Schwefel als H2S vorhanden ist.
10. Katalysator nach einem der vorangehenden Ansprüche, wobei die nichtoxydierende Atmosphäre eine Mischung aus H2 und H2S umfaßt.
11. Katalysator nach einem der vorangehenden Ansprüche, wobei die erhöhte Temperatur mindestens etwa 200°C ist.
12. Katalysator nach einem der vorangehenden Ansprüche, der auf einem hitzebeständigen, anorganischen Oxidträger aufgebracht ist.
13. Selbstaktivierter Molybdän- und/oder Wolframsulfid-Trägerkatalysator nach einem der Ansprüche 2 bis 12, der gebildet wird, indem (a) ein hitzebeständiger anorganischer Oxidträger mit einem oder mehreren wasserlöslichen Katalysatorvorläufersalzen zusammengebracht wird und das Verbundmaterial in einer nicht oxydierenden Atmosphäre in Gegenwart von Schwefel ausreichend lange auf eine erhöhte Temperatur erhitzt wird, um den Katalysator zu bilden, dadurch gekennzeichnet, daß das oder jedes wasserlösliche Katalysatorvorläufersalz die Formel (ML)(MoyW1-yO4) hat, in der M ein oder mehrere zweiwertige aus Fe, Co, Zn, Ni, Cu, Mn und deren Mischungen ausgewählte Promotormetalle umfaßt, y ein Wert im Bereich von 0 bis 1 ist und L ein oder mehrere neutrale stickstoffhaltige Liganden, von denen mindestens einer ein chelatisierender mehrzähniger Ligand ist, bedeutet.
14. Verfahren zur Herstellung des selbstaktivierten Trägerkatalysators nach Anspruch 13, bei dem:
(i) ein poröser hitzebeständiger anorganischer Oxidträger mit einem wasserlöslichen Katalysatorvorläufersalz zusammengebracht wird und
(ii) das in Schritt (i) gebildete Verbundmaterial in einer nichtoxydierenden Atmosphäre in Gegenwart von Schwefel in Form von einer oder mehrerer schwefeltragender Verbindungen auf eine erhöhte Temperatur, vorzugsweise auf eine Temperatur von mindestens etwa 200°C, erwärmt wird, um den Katalysator zu bilden, dadurch gekennzeichnet, daß das wasserlösliche Katalysatorvorläufersalz die Formel (ML)(MoyW1-yO4) hat, in der M ein oder mehrere zweiwertige aus Mn, Fe, Co, Ni, Cu, Zn und deren Mischungen ausgewählte Promotormetalle umfaßt, y ein Wert im Bereich von 0 bis 1 ist und L ein oder mehrere neutrale stickstoffhaltige Liganden, von denen mindestens einer ein chelatisierender mehrzähniger Ligand ist, bedeutet.
15. Verfahren nach Anspruch 14, bei dem der Träger Aluminiumoxid umfaßt.
16. Verfahren nach Anspruch 14, bei dem der Träger Chromoxid umfaßt.
17. Verfahren nach Anspruch 16, bei dem der Chromoxidträger auf ein hitzebeständiges, anorganisches Oxidträgermaterial aufgebracht ist.
EP85306935A 1984-12-11 1985-09-27 Selbstaktivierender Hydrierkatalysator Expired EP0186938B1 (de)

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JPH0550345B2 (de) 1993-07-28
CA1251193A (en) 1989-03-14
EP0186938A1 (de) 1986-07-09
US4595672A (en) 1986-06-17
DE3570047D1 (en) 1989-06-15

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